Ketone and method of making same



Patented Nov. 26, 1929 UNITED STATES PATENT OFFICE CHABLOTTENBUBG, GERMANY, ASSIGNORS TO THE FIRM AKTIENGFSELLSCHAFT, OF BERLIN, GERMANY SGHERING-KAHLBAUM KETONE AND METHOD OF MAKING SAME 1T0 Drawing. Application filed December m, 1927, Serial No. 240,612, and in Germany December 15, 1928.

Our invention relates to a new composition of matter, being a ketone, and to the method of making this and similar ketones.

Up to this day the addition of organic acid chlorides to ethylene only led to the corresponding unsaturated ketones, inasmuch as the alkyl-fl-halogen ethyl ketoneswhich may be assumed to be formed as intermediate products, show a great tendency to split off hydrochloric acid. Thus, for instance, Krapiwin (Chemisches Zentralblatt 1910, I. 1336) obtained from acetyl chloride and ethylene only the unsaturated ketone, viz butenone. Only some of the higher olefines show intermediate products having greater stability.

We have now ascertained the surprising 4 fact that such intermediate products can be obtained with a good yield also when effecting the addition of ethylene to organic acid chlorides, if acyl halogenides are treated with ethylene in the presence of condensation agents or catalysts, such as anhydrous aluminium halogenide or iron halogenide, water to be added to the mass at the end of the reaction, preferably under cooling, and the halogen ketone formed being separated or being extracted by lixiviation with an organic solvent.

The reaction occurs according to the formula The reaction can also be carried out in the presence of solvents or diluents, for instance a surplus of acyl halogenide or other means such as chloroform, hexane, nitrobenzene be ing used.

Example 1Methyl-B-c'klloro ethyl ketone Into 100 to 200 parts acetyl chloride dry ethylene is introduced during some hours under coolin and stirring together with the adual a dition of 133 parts aluminium The compound is a limpid and colorless oil, boiling at C. under 16 mms. mercury pressure and having a very pregnant smell. WVhen allowed to stand for a longer time, it gradually assumes a dark color.

Ewamplc 2-Methyl-,B-lbromo ethyl ketone The production of this compound is effected 1n analogy to Example 1, ethylene being made to react with acetyl bromide in the presence of aluminium bromide. The smell of this compound closely resembles that of the corresponding chlorine compound. The boiling point of the product is 55-60 C. under 15 mms. mercury pressure.

. I Example 3 To parts acetyl chloride are added under vigorous stirring and cooling 81 parts of.

anhydrous sublimated iron chloride in portions. At the same time dry ethylene is introduced and further 60 parts acetyl chloride are gradually added in drops. The product of reaction is poured into cold water and is shaken with ether. On the dried ether being distilled off, there remains over the methyl-[3- chloro ethyl ketone described in Example 1.

Example 4 layer is preferably once more shaken with ether. The organic solvents are dried and subjected to distillation and leave over the 99 methyl-,B-chloro ethyl ketone.

" Emample 5 To 100 parts propionyl chloride are added in small portions and under stirrin 50 grams of finely powdered aluminium ch oride, the mixture being cooled with ice and ethylene being simultaneously introduced. The mixture is treated further as described with reference to Example 1. One obtains'ethyl- 109 tures.

fl-chloro ethyl ketone boiling at 48-56 C. under 13 mms. mercury pressure.

Various changes may be made in the details disclosed in the foregoing specification without departing from the invention or sacrificing the advantages thereof.

We claim 1. 'As a new product, methyl-B-bromo ethyl ketone, being a limped colorless oil having a very pregnant smell and boiling at -60 C. under 15 mms. mercur pressure, the'compound having the form a 2. Method of producing alkyl-B-halogen ethyl ketones, comprising causing ethylene to act on acyl halogenide in the presence of a condensing agent and treating the reaction product with water.

3. Method of producing alkyl-B-halogen ethyl ketones, comprising causing ethylene to act on acyl halogenide in the presence of a condensing agent and treating the reaction product with water under cooling.

4. Method of producing alky ethyl ketones, comprising causing ethylene to act on acyl halogenide in the presence of a condensing agent and a solvent and treat-- ing the reaction product with water.

5. Method of producing alkyl-B halogen ethyl ketones, comprising causing ethylene to act on acyl halogenide in the presence of a condensing agent and a diluent and treating the reaction product with water.

6. Method of producing alkyl-B-halogen ethyl ketones, comprising causing ethylene to act on acyl halogenide in the presence of an anhydrous metal halogenide, and treatin the reaction product with water.

. Method of producing alkyl-B-halogen ethyl ketones, comprising causing ethylene to act on acyl halogenide in the presence of an anhydrous aluminium halogenide and treatin the reaction productwith water.

11 testimony whereof we aflix our signa- WALTER SOHOELLER. OLEMENSZOLLNER.

l-fi-halogen I 

